EP0887707B1 - Positiv-Fotoresist-Zusammensetzung - Google Patents

Positiv-Fotoresist-Zusammensetzung Download PDF

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Publication number
EP0887707B1
EP0887707B1 EP98111548A EP98111548A EP0887707B1 EP 0887707 B1 EP0887707 B1 EP 0887707B1 EP 98111548 A EP98111548 A EP 98111548A EP 98111548 A EP98111548 A EP 98111548A EP 0887707 B1 EP0887707 B1 EP 0887707B1
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EP
European Patent Office
Prior art keywords
group
groups
carbon atoms
resin
alkali
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EP98111548A
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English (en)
French (fr)
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EP0887707A1 (de
Inventor
Shiro Tan
Toshiaki Aoai
Toru Fujimori
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP9167405A external-priority patent/JPH1115161A/ja
Priority claimed from JP9267026A external-priority patent/JPH11109629A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0887707A1 publication Critical patent/EP0887707A1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/115—Cationic or anionic

Definitions

  • the present invention relates to a positive photoresist composition for use in the production of semiconductor IC elements, masks for IC production, printed circuit boards, liquid-crystal panels, etc.
  • a chemically amplified positive resist composition is a pattern-forming material in which an acid generates in exposed areas upon irradiation with a radiation such as far ultraviolet rays and this acid catalyzes a reaction that makes the areas irradiated with the actinic rays and the unirradiated areas to differ in solubility in a developing solution to thereby form a pattern on a substrate.
  • Examples thereof include combinations of a compound which generates an acid upon photodecomposition with an acetal or O,N-acetal compound (see JP-A-48-89003; the term "JP-A” as used herein means an "unexamined published Japanese patent application”), with an orthoester or amidoacetal compound (see JP-A-51-120714), with a polymer having acetal or ketal groups in the backbone (see JP-A-53-133429), with an enol ether compound (see JP-A-55-12995), with an N-acyliminocarbonic acid compound (see JP-A-55-126236), with a polymer having orthoester groups in the backbone (see JP-A-56-17345), with a tertiary alkyl ester compound (see JP-A-60-3625), with a silyl ester compound (see JP-A-60-10247), and with a silyl ether compound (see JP-A-60
  • Another means for eliminating the problem described hereinabove is a system which is stable over long at room temperature but decomposes upon heating in the presence of an acid to become alkali-soluble.
  • Examples thereof include systems comprising a combination of a compound which generates an acid upon exposure to light with an ester having a tertiary or secondary carbon (e.g., t-butyl or 2-cyclohexenyl) or with a carbonic ester compound, as described in, e.g., JP-A-59-45439, JP-A-60-3625, JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642; Polym. Eng. Sce.
  • the chemically amplified positive resist compositions described above are roughly divided into three groups: three-component systems comprising an alkali-soluble resin, a compound which generates an acid upon exposure to a radiation (photo-acid generator), and a dissolution inhibitive compound for the alkali-soluble resin which has acid-decomposable groups; two-component systems comprising a resin having groups which decompose upon reaction with an acid to render the resin alkali-soluble and a photo-acid generator; and hybrid systems comprising a resin having groups which decompose upon reaction with an acid to render the resin alkali-soluble, a low-molecular dissolution inhibitive compound having an acid-decomposable group, and a photo-acid generator.
  • JP-A-2-19847 is disclosed a resist composition characterized by containing a resin obtained from poly(p-hydroxystyrene) by protecting all or part of the phenolic hydroxyl groups each with a tetrahydropyranyl group.
  • JP-A-4-219757 is disclosed a resist composition characterized by containing a resin obtained likewise from poly(p-hydroxystyrene) by replacing from 20 to 70% of the phenolic hydroxyl groups each with an acetal group.
  • JP-A-5-249682 discloses a photoresist composition containing a similar resin protected with an acetal.
  • JP-A-8-123032 is disclosed a photoresist composition containing a terpolymer having groups substituted with acetal groups.
  • JP-A-8-253534 discloses a photoresist composition containing a partly crosslinked polymer having groups substituted with acetal groups.
  • JP-A-8-15864 discloses a positive resist composition
  • a positive resist composition comprising a mixture comprising as a resin component polyhydroxystyrene in which 10 to 60 mol% of hydroxy groups were replaced with t-butoxycarbonyloxy groups and polyhydroxystyrene in which 10 to 60 mol% of hydroxy groups were replaced with ethoxyethoxy groups.
  • compositions have some problems such as unsatisfactory dimensional reproducibility of isolated patterns and generation of scum at lower parts of patterns after development. Solution of these problems has been desired.
  • An object of the present invention is to provide an excellent, chemically amplified positive photoresist composition which has high resolution and improved dimensional reproducibility of isolated patterns.
  • Another object of the present invention is to provide an excellent, chemically amplified positive photoresist composition which is prevented from generating a scum after development and has high resolution.
  • a positive photoresist composition comprising a combination of two alkali-soluble resin binders each having a substituent having a different specific structure from each other, a compound which generates an acid upon irradiation with actinic rays or a radiation, and a solvent (first photoresist composition) shows high resolution and is effective in eliminating the above-described problem concerning the dimensional reproducibility of isolated patterns
  • a positive photoresist composition comprising a combination of an alkali-soluble resin binder substituted with substituents of a specific structure and a nonpolymeric dissolution inhibitive compound having specific functional groups, a compound which generates an acid upon irradiation with actinic rays or a radiation, and a solvent (second photoresist composition) shows high resolution and is effective in eliminating the problem of scum generation described above.
  • the present invention has been completed based on these findings.
  • the alkali-soluble resin having phenolic hydroxyl groups used for the present invention is preferably a copolymer of o-, m-, or p-hydroxystyrene (these are inclusively referred to as hydroxystyrenes) or o-, m-, or p-hydroxy- ⁇ -methylstyrene (these are inclusively referred to as hydroxy- ⁇ -methylstyrenes) in which the content of repeating units derived from the styrene derivative is at least 30 mol%, preferably at least 50 mol%, a homopolymer of any of these styrene derivatives, or a resin obtained by partially hydrogenating the benzene nuclei of those units of the copolymer or homopolymer.
  • This alkali-soluble resin has a weight-average molecular weight in the range of preferably from 3,000 to 80,000, more preferably from 7,000 to 50,000.
  • the molecular weight distribution (M w /M n ) thereof is in the range of generally from 1.01 to 4.0, preferably from 1.05 to 1.20.
  • a polymerization technique such as anionic polymerization is preferably used for obtaining a polymer having such a molecular weight distribution.
  • Resin A obtained from the alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the phenolic hydroxyl groups each with a group represented by formula (I) given above.
  • R 1 represents a substituent selected from alkyl groups having 1 to 4 carbon atoms.
  • W represents either an organic group containing at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and silicon atoms or an atomic group selected from the group consisting of an amino group, an ammonium group, and a mercapto group.
  • n represents a natural number of from 1 to 4, preferably 2 or 3.
  • R 1 examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. More preferred is methyl.
  • the organic group represented by W comprises at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and silicon atoms and at least one carbon atom.
  • W include groups represented by the following formulae. -OR 2 -CH(COOR 2 ) 2 -C(COOR 2 ) 3 -CH 2 COOR 2 -N(COOR 2 ) 2 -CH(CONHR 2 ) 2 -C(CONHR 2 ) 3 -CH 2 CONHR 2 -N(CONHR 2 ) 2 -CN -SR 2 -CHO
  • Preferred examples of the linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms which is represented by R 2 or R 3 include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, and cyclohexyl. More preferred are methyl and ethyl.
  • Preferred examples of the linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms which is represented by R 2 include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl, and cyclohexenyl. More preferred are vinyl and isopropenyl.
  • Preferred examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, mesityl, and cumenyl, with phenyl being more preferred.
  • Preferred examples of the aralkyl group having 7 to 13 carbon atoms include benzyl, phenethyl, ⁇ -methylbenzyl, and benzhydryl, with benzyl being more preferred.
  • aryl and aralkyl groups may have one or more substituents selected from halogen atoms, nitro, alkoxy, acetyl, amino, ester, and amido groups, and the like.
  • Preferred examples of the linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms which is represented by R 3 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and hexyloxy. More preferred are methoxy and ethoxy.
  • Preferred examples of the-halogen atom include fluorine, chlorine, bromine, and iodine. More preferred are chlorine and bromine.
  • W may be a cyano or formyl group.
  • Resin A having the substituents described above, can be obtained by synthesizing the vinyl ether corresponding to the substituents and reacting the ether by a known method with an alkali-soluble resin containing phenolic hydroxyl groups which has been dissolved in an appropriate solvent, e.g., tetrahydrofuran. This reaction is usually conducted in the presence of an acid catalyst, preferably an acid ion-exchange resin, hydrochloric acid, or p-toluenesulfonic acid, or a salt such as pyridinium tosylate.
  • the corresponding vinyl ether can be synthesized from an active starting material such as chloroethyl vinyl ether through a nucleophilic substitution reaction or the like.
  • Resin A for use in the present invention should not be construed as being limited to these examples, in which Me represents methyl, Et ethyl, Ph phenyl, tBu t-butyl, and Ac acetyl.
  • the substituent R 4 in formula (II) or (III) given above is an alkyl group having 1 to 6 carbon atoms, specifically, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms specifically, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.
  • examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, cyclopentyl, n-hexyl, isohexyl, and cyclohexyl.
  • Preferred among these are tertiary alkyl groups such as t-butyl and t-pentyl.
  • Resin B for use in the present invention should not be construed as being limited to these examples, in which Me represents methyl, Et ethyl, Ph phenyl, tBu t-butyl, and Ac acetyl.
  • Resin A contained in the first composition according to the present invention from 10 to 80%, preferably from 15 to 60%, more preferably from 20 to 40%, of the phenolic hydroxyl groups of the alkali-soluble resin should have been replaced with substituents represented by formula (I).
  • Resin B should be one in which from 10 to 80%, preferably from 15 to 60%, more preferably from 20 to 40%, of the phenolic hydroxyl groups of the alkali-soluble resin have been replaced with substituents represented by formula (II) or (III).
  • Resin B in the present invention may contain both or either of substituents represented by formula (II) and substituents represented by formula (III).
  • Resin A according to the present invention which is obtained by protecting phenolic hydroxyl groups (alkali-soluble groups) of an alkali-soluble resin with specific acid-decomposable groups represented by formula (I), produces remarkable effects when used in combination with Resin B, which has been protected with specific acid-decomposable groups represented by formula (II) or (III).
  • Resin B can be synthesized by the following methods. In the case where substituents represented by formula (II) are introduced into an alkali-soluble resin containing phenolic hydroxyl groups, this is accomplished by reacting the alkali-soluble resin with, for example, t-butyl bromoacetate by a known method to replace part of the phenolic hydroxyl groups with t-butyl ester groups, thereby giving Resin B.
  • Resin A and Resin B each has a weight-average molecular weight of preferably from 3,000 to 80,000, more preferably from 7,000 to 50,000.
  • the molecular weight distribution (M w /M n ) thereof is in the range of generally from 1.01 to 4.0, preferably from 1.05 to 1.20.
  • Resin A and Resin B in combination, as in the present invention, is novel.
  • the protective groups represented by formulae (I), (II), and (III) contained in these resins decompose by the action of an acid and thus function to enhance solubility of each resin in an alkaline developing solution.
  • the mixing weight ratio of Resin A to Resin B is preferably from 20/80 to 80/20, more preferably from 30/70 to 70/30, most preferably from 40/60 to 60/40.
  • Resin A should be one in which from 10 to 80%, preferably from 10 to 60%, more preferably from 10 to 40%, of the phenolic hydroxyl groups of the alkali-soluble resin should have been replaced with substituents represented by formula (I).
  • Resin A which is obtained by protecting phenolic hydroxyl groups (alkali-soluble groups) of an alkali-soluble resin with specific acid-decomposable groups represented by formula (I), produces remarkable effects when used in combination with a nonpolymeric dissolution inhibitive compound.
  • the second composition according to the present invention should further contain a nonpolymeric dissolution inhibitive compound which has at least one kind of group selected from tertiary alkyl ester groups and tertiary alkyl carbonate groups and capable of increasing the solubility of the resin in aqueous alkali solutions by the action of an acid.
  • a nonpolymeric dissolution inhibitive compound which has at least one kind of group selected from tertiary alkyl ester groups and tertiary alkyl carbonate groups and capable of increasing the solubility of the resin in aqueous alkali solutions by the action of an acid.
  • the nonpolymeric dissolution inhibitive compound means a compound which has a structure formed by incorporating one or more acid-decomposable groups selected from those mentioned above into a compound having a certain molecular weight not higher than 3,000 and having a single structure, and which becomes alkali-soluble by the action of an acid.
  • This nonpolymeric dissolution inhibitive compound preferably has, per molecule, three or more groups decomposable by an acid and becomes alkali-soluble upon decomposition of these groups.
  • the resin and nonpolymeric dissolution inhibitive compound described above can be used in combination with an alkali-soluble resin containing no acid-decomposable groups.
  • the nonpolymeric dissolution inhibitive compound, component (b), used in the present invention has at least one kind of acid-decomposable group selected from tertiary alkyl ester groups and tertiary alkyl carbonate groups, and may have these two kinds of groups in combination.
  • each structure has at least two acid-decomposable groups and the two acid-decomposable groups most apart from each other are separated from each other by at least 10, preferably at least 11, more preferably at least 12 bonding atoms excluding those contained in the acid-decomposable groups, or to use a compound in which each structure has at least three acid-decomposable groups and the two acid-decomposable groups most apart from each other are separated from each other by at least 9, preferably at least 10, more preferably at least 11 bonding atoms excluding those contained in the acid-decomposable groups.
  • the nonpolymeric dissolution inhibitive compound inhibits the dissolution of the alkali-soluble resin in an alkali, but upon exposure to light it functions to accelerate the dissolution of the resin in an alkali because the protective acid-decomposable groups thereof are eliminated by an acid generated upon exposure.
  • dissolution inhibitive compounds having the skeletons of naphthalene, biphenyl, and a diphenylcycloalkane are disclosed in JP-A-63-27829 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") and JP-A-3-198059, these compounds are less effective in inhibiting the dissolution of alkali-soluble resins and are insufficient in profile and resolution.
  • nonpolymeric dissolution inhibitive compound for use in the present invention include a compound obtained from a single-structure compound having a molecular weight of 3,000 or lower and containing three or more alkali-soluble groups per molecule by protecting at least half of the alkali-soluble groups with acid-decomposable groups selected from the aforementioned ones.
  • Use of such a nonpolymeric dissolution inhibitive compound containing alkali-soluble groups remaining unprotected is advantageous in that it has improved solubility in solvents and thus enhances the effects of the invention.
  • the upper limit of the number of those bonding atoms is preferably 50, more preferably 30.
  • the nonpolymeric dissolution inhibitive compound for use in the present invention has a significantly improved dissolution inhibitive effect on the alkali-soluble resin when it has three or more, preferably four or more acid-decomposable groups, or when it has two acid-decomposable groups and these acid-decomposable groups are apart from each other at not less than a certain distance.
  • the distance between acid-decomposable groups in the present invention is expressed in terms of the number of bonding atoms present between the groups, excluding the atoms contained in the groups. For example, in each of compounds (1) and (2) shown below, the distance between acid-decomposable groups is 4 bonding atoms. In compound (3), that distance is 12 bonding atoms.
  • the acid-decomposable dissolution inhibitive compound for use in the present invention may have two or more acid-decomposable groups on the same benzene ring, it is preferably a compound having a framework in which each benzene ring does not have more than one acid-decomposable group.
  • the molecular weight of the acid-decomposable dissolution inhibitive compound for use in the present invention is 3,000 or lower, preferably from 500 to 3,000, more preferably from 1,000 to 2,500.
  • the acid-decomposable group is bonded to the compound in the form of the structure represented by -COO-C(R 01 )(R 02 )(R 03 ) or -O-CO-O-C(R 01 )(R 02 )(R 03 ), more preferably the structure represented by -R 0 -COO-C(R 01 )(R 02 )(R 03 ) or -Ar-O-CO-O-C(R 01 )(R 02 )(R 03 ).
  • R 01 , R 02 , and R 03 may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Two of R 01 to R 03 may be bonded to each other to form a ring, while it is preferred not to form a ring.
  • R 0 and Ar represents an optionally substituted, aliphatic or aromatic hydrocarbon group having a valence of 2 or higher.
  • the alkyl group is preferably one having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.
  • the cycloalkyl group is preferably one having 3 to 10 carbon'atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, or adamantyl.
  • the alkenyl group is preferably one having 2 to 4 carbon atoms, such as vinyl, propenyl, allyl, or butenyl.
  • the aryl group is preferably one having 6 to 14 carbon atoms, such as phenyl, xylyl, toluyl, cumenyl, naphthyl, or anthracenyl.
  • substituents include hydroxy, halogen atoms (fluorine, chlorine, bromine, and iodine), nitro, cyano, the alkyl groups enumerated above, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, sec-butoxy, and t-butoxy, alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl, aralkyl groups such as benzyl, phenethyl, and cumyl, aralkyloxy groups, acyl groups such as formyl, acetyl, butyryl, benzoyl, cyanamyl, and valeryl, acyloxy groups such as butyryloxy, the alkenyl groups enumerated above, alkenyloxy groups such as vinyloxy, propenyloxy, allyloxy, and butenyloxy, the aryl
  • tertiary alkyl group contained in the tertiary alkyl ester groups and tertiary alkyl carbonate groups include t-butyl, t-pentyl and t-hexyl, and especially, t-butyl.
  • nonpolymeric dissolution inhibitive compound as component (b) examples include compounds obtained from the polyhydroxy compounds given in the patent documents specified below by protecting part or all of the phenolic OH groups by bonding thereto the tertiary alkyl ester groups and tertiary alkyl carbonate groups; the patent documents include JP-A-1-289946, JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4-12356, JP-A-4-
  • Preferred of these are the compounds obtained from the polyhydroxy compounds given in JP-A-1-289946, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-200251, JP-A-3-200252, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP-A-4-12356, JP-A-4-12357, Japanese Patent Applications Nos. 4-25157, 4-103215, 4-104542, 4-107885, 4-107889, and 4-152195.
  • polyhydroxy compounds are represented by formulae (I) to (XVI).
  • R represents a hydrogen atom, -CH 2 -COO-C(CH 3 ) 2 C 6 H 5 , -CH 2 -COO-C(CH 3 ) 3 , or -COO-C(CH 3 ) 3 , provided that at least two or, depending on the structure, at least three of R's are not hydrogen atoms, and that the substituents represented by R need not be the same.
  • the addition amount of the dissolution inhibitive compound is from 3 to 50% by weight, preferably from 5 to 35% by weight based on the total amount of all solid components of the photosensitive composition. If the amount is less than 3%, high resolution may not be obtained. If it exceeds 50%, there is a tendency that the storage stability is deteriorated to cause film shrinkage and the heat resistance of the resist is deteriorated.
  • the first and second compositions can contain an alkali-soluble resin having no acid-decomposable groups.
  • the addition of such an alkali-soluble resin improves the sensitivity.
  • the alkali-soluble resin having no acid-decomposable groups (hereinafter referred to also as "alkali-soluble resin”) is a resin soluble in an aqueous alkali solution. Preferred examples thereof include polyhydroxystyrenes, novolak resins and derivatives thereof. Copolymers containing p-hydroxystyrene units can be used as long as they are alkali-soluble.
  • poly(p-hydroxysyrene), poly(p/m-hydroxystyrene) copolymer, poly(p/o-hydroxystyrene) copolymer, and poly(p-hydroxystyrene-styrene) copolymer are especially preferred.
  • Poly(alkyl-substituted hydroxystyrene) resins such as poly(4-hydroxy-3-methylstyrene) resin and poly(4-hydroxy-3,5-dimethylstyrene) resin, and resins prepared by alkylating or acetylating part of phenolic OH groups of the above-described resins are also preferably used as long as they are alkali-soluble.
  • the resins in which part of phenol nuclei of the above resins (30 mol% or less of the whole phenol nuclei) are hydrogenated have improved transparency and are preferable in sensitivity, resolution and formation of rectangular profile.
  • alkali-soluble resin for use in the present invention examples include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, polyhydroxystyrene, alkyl-substituted polyhydroxystyrene, hydroxystyrene/N-substituted maleimide copolymers, partially O-alkylated poly(hydroxystyrene)s, partially O-acylated poly(hydroxystyrene)s, styrene/maleic anhydride copolymers, carboxylated methacrylic resins, and derivatives thereof, poly(styrene-hydroxystyrene) copolymer, and hydrogenated polyhydroxystyrene.
  • the alkali-soluble resin for use in the present invention should not be construed as being limited to these examples.
  • alkali-soluble resins include novolak resins, alkali-soluble resins containing p-hydroxystyrene units (preferably poly(p-hydroxystyrene), poly(p/m-hydroxystyrene) copolymer, poly(p/o-hydroxystyrene) copolymer, poly(p-hydroxystyrene-styrene) copolymer, poly(alkyl-substituted hydroxystyrene) resins such as poly(4-hydroxy-3-methylstyrene) resin and poly(4-hydroxy-3,5-dimethylstyrene) resin, and resins prepared by alkylating or acetylating part of phenolic OH groups of the above-described resins, partially hydrogenated polyhydroxystyrene resins, polyhydroxystyrene resins, partially hydrogenated novolak resins, and partially hydrogenated polyhydroxystyrene resins.
  • p-hydroxystyrene units
  • polyhydroxystyrene means a polymer obtained by polymerizing at least one monomer selected from the group consisting of p-hydroxystyrene monomer, m-hydroxystyrene monomer, o-hydroxystyrene monomer, and alkyl-substituted hydroxystyrene monomers in which the above-described monomers are substituted by an alkyl group having 1 to 4 carbon atoms at the ortho-position with respect to the hydroxyl group thereof.
  • the novolak resins are obtained by addition-condensing one or more given monomers as the main ingredient with one or more aldehydes in the presence of an acid catalyst.
  • Examples of the given monomers include hydroxylated aromatic compounds such as phenol, cresols, i.e., m-cresol, p-cresol, and o-cresol, xylenols, e.g., 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol, alkylphenols, e.g., methylphenol, p-ethylphenol, o-ethylphenol, p-t-butylphenol, p-octylphenol, and 2,3,5-trimethylphenol, alkoxyphenols, e.g., p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, and p-butoxyphenol
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde, ⁇ -phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloro
  • aldehydes may be used alone or in combination of two or more thereof.
  • the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, and oxalic acid.
  • the addition amount of the alkali-soluble resin containing no acid-decomposable groups is preferably up to 50% by weight, more preferably up to 30% by weight, most preferably up to 20% by weight, based on the total amount of the alkali-soluble resin containing no acid-decomposable groups and the alkali-soluble resin containing an acid-decomposable group.
  • the photo-acid generator (c) is a compound which generates an acid by the irradiation of an actinic ray or radiation.
  • photo-acid generators usable in combination with the specific photo-acid generator include photoinitiators for cationic photopolymerization, photoinitiators for radical photopolymerization, photodecolorants for dyes, optical color changers, and known compounds which generate an acid by the action of known light which is used in microresists, etc. such as ultraviolet ray having a wavelength of 400 to 200 nm, far-ultraviolet ray, especially, g-line, h-line, i-line, KrF exima laser light), ArF exima laser light, electron beam, X-ray, molecule ray, or ion beam.
  • photo-acid generators may be suitably used either alone or as a mixture of two or more thereof.
  • onium salts such as: the diazonium salts described in, e.g., S.I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974) and T.S. Bal et al., Polymer , 21, 423 (1980); the ammonium salts described in, e.g., U.S. Patents 4,069,055 and 4,069,056, U.S. Reissued Patent 27,992, and Japanese Patent Application No. 3-140,140; the phosphonium salts described in, e.g., D.C. Necker et al., Macromolecules , 17, 2468 (1984), C.S. Wen et al., Teh, Proc. Conf. Rad.
  • onium salts such as: the diazonium salts described in, e.g., S.I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974) and T.S. Bal et al., Polymer , 21, 4
  • Patent 3,905,815, JP-B-46-4605 (the term "JP-B” as used herein means an "examined Japanese patent publication"), JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339; the organometallic compound/organic halide combinations described in, e.g., K. Meier et al., J. Rad. Curing , 13 (4), 26 (1986), T.P.
  • a compound obtained by incorporating such groups or compounds which generate an acid by the action of light into the backbone or side chains of a polymer can be used.
  • this polymeric compound are given in, e.g., M.E. Woodhouse et al., J. Am. Chem. Soc ., 104, 5586 (1982), S.P. Pappas et al., J. Imaging Sci ., 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., Rapid Commun ., 9,625 (1988), Y. Yamada et al., Makromol. Chem ., 152, 153, 163 (1972), J.V.
  • Ar 3 and Ar 4 each independently represents a substituted or unsubstituted aryl group;
  • R 206 represents a substituted or unsubstituted alkyl or aryl group; and
  • A represents a substituted or unsubstituted alkylene, alkenylene, or arylene group.
  • the substituted aryl group as Ar 3 and Ar 4 preferably has 6 to 18 carbon atoms.
  • the substituent include a halogen atom, an alkyl group such as methyl, ethyl, propyl and butyl, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, and a trifluoromethyl group.
  • Preferred examples of the unsubstituted aryl group as Ar 3 and Ar 4 include those having 6 to 10 carbon atoms such as phenyl and naphthyl.
  • the unsubstituted alkyl group as R 206 is preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • the unsubstituted aryl group as R 206 is preferably an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl.
  • the substituted alkyl and aryl groups preferably have 6 to 14 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, a cycloalkyl group and a trifluoromethyl group, each haying 1 to 8 carbon atoms, and a halogen atom.
  • the unsubstituted alkylene, alkenylene, or arylene group as A preferably has 2 to 10 carbon atoms
  • the substituted alkylene, alkenylene, or arylene group as A preferably has 2 to 14 carbon atoms.
  • the substituent include an alkyl group,-an alkoxy group, a cycloalkyl group, each having 1 to 6 carbon atoms, a phenyl group, a trifluoromethyl group, and a halogen atom.
  • Compound (c) which generates an acid with irradiation of actinic ray or radiation is selected from the onium salts, disulfones, 4-position DNQ sulfonates, and triazine compounds.
  • the addition amount of Compound (c) is generally from 0.001 to 40 % by weight, preferably from 0.01 to 20 % by weight, more preferably from 0.1 to 5 % by weight, based on the total weight (excluding a coating solvent) of the positive photoresist composition. If the amount is less than 0.001 % by weight, the sensitivity is reduced, and if it exceeds 40 % by weight, light absorption of the resist is increased to thereby deteriorate the profile or reduce process (especially bake) margin.
  • composition of the present invention can contain organic basic compounds, which improve the stability during storage and reduce the change in line width attributable to PED.
  • Desirable organic basic compounds usable in the present invention are compounds which are more strongly basic than phenol, in particular, nitrogen-containing basic compounds.
  • Preferred chemical environments include structures represented by the following formulae (A) to (E).
  • Preferred organic basic compounds are nitrogen-containing basic compounds having, per molecule, two or more nitrogen atoms having different chemical environments. Especially preferred are compounds containing both at least one substituted or unsubstituted amino group and at least one nitrogen-containing ring structure and compounds having at least one alkylamino group.
  • Examples of such preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridines, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, and substituted or unsubstituted aminoalkylmorpholines.
  • Preferred substituents include amino, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups, alkoxy groups, acyl groups, acyloxy groups, aryl groups, aryloxy groups, nitro, hydroxy, and cyano.
  • organic basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazo
  • nitrogen-containing basic compounds may be used alone or in combination of two or more thereof.
  • the use amount of the nitrogen-containing basic compounds is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount thereof is smaller than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, reduced sensitivity and impaired developability at unexposed parts are liable to be caused.
  • the chemically amplified positive resist composition can further contain a surfactant, dye, pigment, plasticizer, photosensitizer, or a compound having at least two phenolic OH groups which accelates the solubility in a developing solution, if desired.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, e.g., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers, e.g., polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan/fatty acid esters, e.g., sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene-sorbitan/fatty acid esters, e.g., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorb
  • the surfactant may be added alone or in combination of two or more thereof.
  • the preferred amount of the surfactant is from 0.0005 to 0.01 parts by weight per 100 parts by weight of the composition (excluding a solvent) of the present invention.
  • Dyes suitable for use in the present invention are oil-soluble dyes and basic dyes. Examples thereof include Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries Ltd., Japan), crystal violet (CI 42555), methyl violet (CI 42535), rhodamine B (CI 45170B), malachite green (CI 42000), and methylene blue (CI 52015).
  • Spectral sensitizers such as those given below may be further added to sensitize the photo-acid generator used so as to exhibit absorption in a region of longer wavelengths than far ultraviolet, whereby the photosensitive composition of the present invention can be rendered sensitive to an i- or g-line.
  • spectral sensitizers suitable for use in the present invention include benzophenone, p,p'-tetramethyldiaminobenzophenone, p,p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzil, acridine orange, benzoflavin, cetoflavin T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone,
  • polyhydroxy compounds can be exemplified.
  • Preferred examples thereof include phenols, resorcin, phloroglucin, phloroglucide, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, ⁇ , ⁇ ', ⁇ ''-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, and 1,1'-bis(4-hydroxypheyl)cyclohexane.
  • the photosensitive composition of the present invention is used in the form of a solution in a solvent (component (d)) in which the ingredients described above dissolve.
  • a solvent component (d)
  • the solvent include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, ⁇ -butyrolactone, methyl ethyl ketone, ethylene glycol-monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-di
  • a satisfactory resist pattern can be obtained by applying the photosensitive composition described above on a substrate such as those for use in the production of precision integrated-circuit elements (e.g., silicon/silicon dioxide coating) by an appropriate coating means, e.g., a spinner or coater, exposing the coating to light through a mask, and then baking and developing the coating.
  • a coating means e.g., a spinner or coater
  • an alkaline aqueous solution of an inorganic alkali e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or ammonia water, a primary amine, e.g., ethylamine or n-propylamine, a secondary amine, e.g., diethylamine or di-n-butylamine, a tertiary amine, e.g., triethylamine or methyldiethylamine, an alcoholamine, e.g., dimethylethanolamine or triethanolamine, a quaternary ammonium salt, e.g., tetramethylammonium hydroxide or tetraethylammonium hydroxide, a cyclic amine, e.g., pyrrole or piperidine, or the like.
  • an inorganic alkali e.g., sodium hydroxide, potassium hydroxide, sodium
  • 2-Vinyloxyethylphthalimide represented by the following formula X-3 was obtained from chloroethyl vinyl ether and potassium phthalimide.
  • 2-benzoyloxyethyl vinyl ether which is represented by the following formula X-4, was obtained from chloroethyl vinyl ether and sodium benzoate.
  • the resin obtained had a weight-average molecular weight of 15,000.
  • the resin obtained had a weight-average molecular weight of 12,000.
  • the resin thus obtained was dried in a vacuum dryer at 120°C for 12 hours to obtain a p-hydroxystyrene/methyl methacrylate copolymer as alkali-soluble resin R-3.
  • the resin obtained had a weight-average molecular weight of 10,000.
  • the resultant reaction mixture was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation.
  • the resin thus obtained was dried in a vacuum dryer at 70°C for 12 hours to obtain alkali-soluble resin A-1 having substituents according to the present invention.
  • alkali-soluble resins A-2 to A-10 having substituents according to the present invention were obtained in the same manner as in Synthesis Example III-1.
  • Resins C-1 to C-4 were obtained from the alkali-soluble resins shown in Table 1 given below and from ethyl vinyl ether (Y-1), isobutyl vinyl ether (Y-2), or chloroethyl vinyl ether (Y-3) which are represented by the following formulae in the same manner as in Synthesis Example III-1. No.
  • Alkali-soluble resin R-4 20 g N,N-Dimethylacetamide 80 g Di-t-butyl dicarbonate (Z-1) 7.25 g Triethylamine 16.84 g This mixture was stirred at room temperature for 18 hours.
  • the resultant reaction mixture was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation.
  • the resin thus obtained was sufficiently washed with ultrapure water and then dried in a vacuum dryer at 70°C for 12 hours to obtain alkali-soluble resin B-1 having substituents according to the present invention.
  • the resultant reaction mixture was allowed to cool and then added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation.
  • the resin thus obtained was sufficiently washed with ultrapure water and then dried in a vacuum dryer at 70°C for 12 hours to obtain alkali-soluble resin B-2 having substituents according to the present invention.
  • Alkali-soluble resins B-3 to B-5 having substituents according to the present invention were obtained from the alkali-soluble resins shown in Table 2 given below and from di-t-butyl dicarbonate or t-butyl bromoacetate, according to Synthesis Example V-1 or V-2.
  • Synthesis Example No. Resin Alkali-Soluble Resin Reactant Molecular Weight Molecular Weight Distribution
  • TMAH aqueous tetramethylammonium hydroxide
  • Resolution is expressed in terms of threshold resolution in the exposure amount necessary for reproducing a mask pattern having 0.40 ⁇ m lines and spaces.
  • the reproducibility of isolated patterns in the above exposure amount was evaluated in the following three grades.
  • the resist films which gave isolated patterns having line widths which were from 90 to 100% of the desired line width (0.30 ⁇ m) are rated as,A; those which gave isolated patterns in which the line widths were from 50 to 90% of the desired width are rated as B; and those which gave isolated patterns having line widths below 50% of the desired width or which failed to give isolated patterns are rated as C.
  • No. Threshold Resolution Reproducibility of Isolated Patterns Examples 1 0.25 A 2 0.26 A 3 0.25 A 4 0.25 A 5 0.26 A 6 0.25 A 7 0.26 A 8 0.26 A 9 0.25 A 10 0.25 A Comparative Examples 1 0.27 B 2 0.27 C 3 0.27 B 4 0.27 B 5 0.25 C 6 0.26 C 7 0.26 B 8 0.26 C
  • the resultant reaction mixture was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation.
  • the resin thus obtained was dried in a vacuum dryer at 70°C for 12 hours to obtain alkali-soluble resin A'-1 having substituents according to the present invention.
  • alkali-soluble resins A'-2 to A'-10 having substituents according to the present invention were obtained in the same manner as in Synthesis Example III'-1.
  • Resins C'-1 to C'-4 were obtained from the alkali-soluble resins shown in Table 5 given below and from ethyl vinyl ether (Y-1), isobutyl vinyl ether (Y-2), or chloroethyl vinyl ether (Y-3) which are represented by the following formulae in the same manner as in Synthesis Example III'-1. No.
  • Each ingredient combination shown in Table 2 given below was dissolved in 8 g of PGMEA (propylene glycol monoethyl ether acetate). The resultant solution was filtered through a 0.2 ⁇ m filter to prepare a resist solution. Each resist solution thus obtained was applied to a silicon wafer with a spin coater, and the coating was dried at 130°C for 60 seconds with a vacuum holding type hot plate to obtain a resist film having a thickness of 0.8 ⁇ m. No.
  • TMAH aqueous tetramethylammonium hydroxide
  • Resolution is expressed in terms of threshold resolution in the exposure amount necessary for reproducing a mask pattern having 0.40 ⁇ m lines and spaces.
  • Scum generation was evaluated in the following three grades after each 0.30 ⁇ m pattern obtained in that exposure amount was examined with a scanning electron microscope for a development residue. The patterns in which no scum was observed are rated as A; those in which a scum was observed in lower parts thereof but not observed between lines (i.e., in spaces) are rated as B; and those in which a scum was observed between lines (i.e., in spaces) are rated as C. No.
  • an excellent, chemically amplified positive photoresist composition can be provided which has improved dimensional reproducibility of isolated patterns or is prevented from generating a scum after development while having high resolution.

Claims (6)

  1. Positiv arbeitende Photoresist-Zusammensetzung umfassend:
    (a) Harz A erhältlich aus einem Alkali-löslichen Harz mit phenolischen Hydroxygruppen durch Ersatz von 10 bis 80% der phenolischen Hydroxygruppen jeweils mit einer durch Formel (I) dargestellten Gruppe,
    (b) Harz B erhältlich aus einem Alkali-löslichen Harz mit phenolischen Hydroxygruppen durch Ersatz von 10 bis 80% der phenolischen Hydroxygruppen jeweils mit einer durch Formel (II) oder (III) dargestellten Gruppe,
    (c) eine Verbindung, die bei Bestrahlung mit aktinischen Strahlen oder einer Strahlung eine Säure erzeugt, und
    (d) ein Lösungsmittel,
    Figure 01520001
    Figure 01520002
    Figure 01520003
    worin
    R1 ein aus Alkylgruppen mit 1 bis 4 Kohlenstoffatomen ausgewählter Substituent ist, W entweder einen organischen Rest, der mindestens ein aus Sauerstoff-, Stickstoff-, Schwefel-, Phosphor- und Siliciumatomen ausgewähltes Atom enthält, oder eine Atomgruppe, die aus einer Aminogruppe, einer Ammoniumgruppe und einer Mercaptogruppe ausgewählt ist, darstellt,
    n eine natürliche Zahl von 1 bis 4 ist und
    R4 eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist.
  2. Positiv arbeitende Photoresist-Zusammensetzung nach Anspruch 1, worin W in Formel (I) für Komponente (a) eine Gruppe ist, die aus folgenden Substituenten ausgewählt ist:
    Figure 01530001
    -OR2   -CH(COOR2)2   -C(COOR2)3
    -CH2COOR2   -N(COOR2)2   -CH(CONHR2)2
    -C(CONHR2)3   -CH2CONHR2   -N(CONHR2)2
    Figure 01530002
    -NH2   -N ⁺H3X-
    -SH   -CN   -SR2   -CHO
       worin
    R2 ein Wasserstoffatom oder ein Substituent ausgewählt aus der Gruppe bestehend aus einer linearen, verzweigten oder cyclischen Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einer linearen, verzweigten oder cyclischen Alkenylgruppe mit 2 bis 6 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe und einer substituierten oder unsubstituierten Aralkylgruppe ist,
    R3 ein Wasserstoffatom oder ein Substituent ausgewählt aus der Gruppe bestehend aus einer linearen, verzweigten oder cyclischen Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einer linearen, verzweigten oder cyclischen Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, einem Halogenatom, einer Nitrogruppe, einer Aminogruppe, einer Hydroxygruppe und einer Cyanogruppe ist,
    X ein Halogenatom ist und m eine natürliche Zahl von 1 bis 4 darstellt.
  3. Positiv arbeitende Photoresist-Zusammensetzung nach Anspruch 1 oder 2, worin das Alkali-lösliche Harz mit phenolischen Hydroxygruppen, das für Harz A und/oder Harz B verwendet wird, Poly(p-hydroxystyrol) ist.
  4. Positiv arbeitende Photoresist-Zusammensetzung umfassend:
    (a) Harz A erhältlich aus einem Alkali-löslichen Harz mit phenolischen Hydroxygruppen durch Ersatz von 10 bis 80% der phenolischen Hydroxygruppen jeweils mit einer durch Formel (I) dargestellten Gruppe,
    (b) eine nicht-polymere, Auflösungs-inhibierende Verbindung, die mindestens eine Art von Gruppe ausgewählt aus tertiären Alkylestergruppen und tertiären Alkylcarbonatgruppen aufweist und in der Lage ist, die Löslichkeit in wäßrigen Alkalilösungen durch Einwirkung einer Säure zu erhöhen,
    (c) eine Verbindung, die bei Bestrahlung mit aktinischen Strahlen oder einer Strahlung eine Säure erzeugt, und
    (d) ein Lösungsmittel,
    Figure 01540001
       worin
    R1 ein aus Alkylgruppen mit 1 bis 4 Kohlenstoffatomen ausgewählter Substituent ist, W entweder eine organische Gruppe, die mindestens ein aus Sauerstoff-, Stickstoff-, Schwefel-, Phosphor- und-Siliciumatomen ausgewähltes Atom enthält, oder eine Atomgruppe, die aus einer Aminogruppe, einer Ammoniumgruppe und einer Mercaptogruppe ausgewählt ist, darstellt und n eine natürliche Zahl von 1 bis 4 ist.
  5. Positiv arbeitende Photoresist-Zusammensetzung nach Anspruch 4, worin W in Formel (I) für Komponente (a) eine aus den folgenden Substituenten ausgewählte Gruppe ist:
    Figure 01550001
    -OR2   -CH(COOR2)2   -C(COOR2)3
    -CH2COOR2   -N(COOR2)2   -CH(CONHR2)2
    -C(CONHR2)3   -CH2CONHR2   -N(CONHR2)2
    Figure 01550002
    -NH2   -N ⁺H3X-
    -SH   -CN   -SR2   -CHO
       worin
    R2 ein Wasserstoffatom oder ein Substituent ausgewählt aus der Gruppe bestehend aus einer linearen, verzweigten oder cyclischen Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einer linearen, verzweigten oder cyclischen Alkenylgruppe mit 2 bis 6 Kohlenstoffatomen, einer substituierten oder unsubstituierten Arylgruppe und einer substituierten oder unsubstituierten Aralkylgruppe ist,
    R3 ein Wasserstoffatom oder ein Substituent ausgewählt aus der Gruppe bestehend aus einer linearen, verzweigten oder cyclischen Alkylgruppe mit 1 bis 6 Kohlenstoffatomen, einer linearen, verzweigten oder cyclischen Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, einem Halogenatom, einer Nitrogruppe, einer Aminogruppe, einer Hydroxygruppe und einer Cyanogruppe ist,
    X ein Halogenatom ist und m eine natürliche Zahl von 1 bis 4 ist.
  6. Positiv arbeitende Photoresist-Zusammensetzung nach Anspruch 4 oder 5,
    worin das Alkali-lösliche Harz mit phenolischen Hydroxygruppen, das für Harz A verwendet wird, Poly(p-hydroxystyrol) ist.
EP98111548A 1997-06-24 1998-06-23 Positiv-Fotoresist-Zusammensetzung Expired - Lifetime EP0887707B1 (de)

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JP9167405A JPH1115161A (ja) 1997-06-24 1997-06-24 ポジ型フォトレジスト組成物
JP16740597 1997-06-24
JP167405/97 1997-06-24
JP267026/97 1997-09-30
JP26702697 1997-09-30
JP9267026A JPH11109629A (ja) 1997-09-30 1997-09-30 ポジ型フォトレジスト組成物

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JP4190146B2 (ja) * 2000-12-28 2008-12-03 富士フイルム株式会社 電子線またはｘ線用ポジ型レジスト組成物
DE60238029D1 (de) 2001-12-27 2010-12-02 Shinetsu Chemical Co Resistzusammensetzung und Musterübertragungsverfahren
JP4007581B2 (ja) * 2002-04-19 2007-11-14 富士フイルム株式会社 ポジ型レジスト組成物
KR100881307B1 (ko) * 2004-02-20 2009-02-03 도오꾜오까고오교 가부시끼가이샤 패턴 형성 재료용 기재, 포지티브형 레지스트 조성물 및레지스트 패턴 형성 방법
US7892903B2 (en) * 2004-02-23 2011-02-22 Asml Netherlands B.V. Device manufacturing method and substrate comprising multiple resist layers
JP3946715B2 (ja) * 2004-07-28 2007-07-18 東京応化工業株式会社 ポジ型レジスト組成物およびレジストパターン形成方法
JP4468119B2 (ja) * 2004-09-08 2010-05-26 東京応化工業株式会社 レジスト組成物およびレジストパターン形成方法
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US7981588B2 (en) * 2005-02-02 2011-07-19 Tokyo Ohka Kogyo Co., Ltd. Negative resist composition and method of forming resist pattern
JP5138157B2 (ja) * 2005-05-17 2013-02-06 東京応化工業株式会社 ポジ型レジスト組成物およびレジストパターン形成方法
JP4813103B2 (ja) 2005-06-17 2011-11-09 東京応化工業株式会社 化合物、ポジ型レジスト組成物およびレジストパターン形成方法
JP4732038B2 (ja) 2005-07-05 2011-07-27 東京応化工業株式会社 化合物、ポジ型レジスト組成物およびレジストパターン形成方法
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